CONTRIBUTION OF ELECTRON CORRELATION TO H-BONDS

分子之间的相互作用是造成多种多样的 生物现象，包括蛋白质结构，DNA碱基配对， 疏水效应然而氢键的基本性质， 也许是最具生物学意义的，仍然没有完全理解， 主要基于20世纪70年代开发和应用的分解方法， 使用不太适合此类研究的基组。而且 早期的工作仅限于SCF水平，完全忽略了 电子关联的影响，这是现在已知的是深刻的。的 本项目的目的是剖析氢的相关贡献 绑定到多个组件中; SCF组件也将 计算比过去可靠得多。这些组件将 通过一种新的混合程序进行评估，该程序结合了 分子间和Moller-Plesset超分子微扰理论。的 每个组件的行为将被研究为一些 不同的化学基团通常出现在生物分子中， 各种不同的几何形状。该项目的最终目标是一个基本的 理解氢键的本质。模型潜力将是 开发用于在不可行的情况下协助从头计算， 明确计算相关效应。潜力也将得到利用 水溶液中生物分子的动力学和蒙特卡罗模拟 环境

Interactions between molecules are responsible for a wide diversity of biological phenomena including protein structure, DNA base pairing, and the hydrophobic effect. Yet the fundamental nature of the hydrogen bond, perhaps the most biologically relevant, remains incompletely understood, based largely on decomposition methods developed and applied in the 1970s, using basis sets that were not well-suited to such studies. Moreover, the earlier work was restricted to the SCF level, neglecting completely the effects of electron correlation which are now known to be profound. The present project aims to dissect the correlation contribution to hydrogen bonding into a number of components; the SCF components will also be computed much more reliably than in the past. These components will be evaluated by a new hybrid procedure which combines the best features of intermolecular and Moller-Plesset supermolecular perturbation theory. The behavior of each of the components will be studied for a number of different chemical groups which commonly occur in biomolecules and for a range of different geometries. The ultimate goal of the project is a basic understanding of the nature of the H-bond. Model potentials will be developed to assist in ab initio calculations where it is not feasible to calculate correlation effects explicitly. The potentials will also find use in dynamics and Monte Carlo simulations of biomolecules in aqueous environment.